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Extension of the TBP curve of petroleum using the correlation DESTMOL

Article  in  Procedia Engineering · December 2012

DOI: 10.1016/j.proeng.2012.07.465

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Procedia Engineering 42 (2012) 726 – 732

20th International Congress of Chemical and Process Engineering CHISA 2012

25 – 29 August 2012, Prague, Czech Republic

Extension of the TBP curve of petroleum using the correlation

DESTMOL
M. S. Lopesa, M. Savioli Lopesa, R. Maciel Filhoa, M. R. Wolf Maciela,
L.C. Medinab, a*
a
Separation Process Development Laboratory (LDPS). School of Chemical Engineering. University of Campinas, UNICAMP, P.O.
Box 6066, 13083-970, Campinas-SP, Brazil
b
CENPES/PDP/TPAP/PETROBRAS, Brazil;

Abstract

The properties of natural petroleum and petroleum products make use of the True Boiling Point (TBP) distillation
analysis and it has been proved to be very useful for petroleum characterization and design and operation of refinery
units. So, the TBP distillation analysis has contributed to the petroleum science and technology, to the classification
of petroleum, to the development of petroleum property correlations and it has been used worldwide. However, when
applied to heavy petroleum fractions, difficulties are often encountered. Through petroleum distillation curve (TBP),
it is possible to evaluate the yields of the products that will be obtained in the refineries, as well as to establish
operational strategies and process optimizations, as the cracking process. The TBP curve is very important for the oil
industry and is used to understand the behavior of oil before distillation. For when the oil is subjected to a distillation
tower on an industrial scale is already known about the percentage of distillate obtained working at a specific
temperature. In the oil refining industry as the distillations follow: Atmospheric Distillation (distillation up to 673 K -
ASTM D 2892) and vacuum distillation (distillation to 838K - ASTM D 5236). This work creates the possibility of
extending the temperature range of distillation of oil to 973K. The goal of this work is extend the TBP by
DESTMOL, the extension of the TBP curve oil reaching approximately 973 K exceeding the curves generated so far
that reach only 838 K. The DESTMOL correlation applies pretty good showing continuity and asymptotic profile of
the TBP curve. The results help to meet the waste oil and can thus use the waste for more noble ends. As the result of
DESTMOL, we can better define the strategiesand operating conditions for oil processing, achieving better economic
results in the use of heavy oil, due to its better characterization.

* Corresponding author. Tel.:+55-19-9297-2421; fax:+55-19-3521-3909.

E-mail address: melina@feq.unicamp.br.

1877-7058 © 2012 Published by Elsevier Ltd.

doi:10.1016/j.proeng.2012.07.465
 M. S. Lopes et al. / Procedia Engineering 42 (2012) 726 – 732 727

© 2012 Published by Elsevier Ltd. Selection under responsibility of the Congress Scientific Committee
(Petr Kluson)

Keywords: True boiling point; petroleum; molecular distillation; DESTMOL

1. Introduction

True Boiling Point (TBP) distillation is one of the most common experimental techniques for
determination of petroleum properties. The methods for performing TBP distillation experiments are
described by ASTM D2892 and by ASTM D5236. However, these methods are established for petroleum
fractions that reach temperatures up to 838 K.
In this work, three petroleum residues were distilled in a falling film molecular distillation prototype
and the data were used to obtain the extension of the TBP curve above temperatures of 838 K. It was
possible to extend the TBP curve of these petroleum up to temperatures close to 973K with consistency
and continuity in comparison to the standard curve.
The TBP distillation data were the most commonly available information regarding the volatile
behavior of hydrocarbon mixtures. Specific cut fractions (part of the TBP range), used in the generation of
petroleum products directly influence pricing of crude oils [1]. The other major use of these data is in
deciding refinery processes needed to refine a given crude oil. TBP distillation can also be used as a
method to isolate a specified fraction from a crude oil for testing [2].
Two conventional physical distillation procedures, specified by the American Society for Testing and
Materials (ASTM), are needed for the determination of the boiling range distributions of crude oils. The
first method, ASTM D2892 (American Society of Testing and Materials, 1999a) is suitable for the
distillation of crude oil components boiling at temperatures lower than 673 K. The second method, ASTM
D 5236(American Society of Testing and Materials, 1999b) performed at reduced pressures (0.1 Pa) to
avoid thermal cracking, permits the distillation of crude components boiling at temperatures higher than
673 K. The maximum achievable atmospheric equivalent temperature (AET) with the method ASTM D
5236-95 is 838 K. Curve-fitting mathematical techniques are used to combine the data obtained by the
two methods into a single continuous distillation curve [3].
Recently, the ability of the method to characterize heavy petroleum components with AET higher than
838 K, the maximum achievable temperature by conventional distillation, has been exploited. A
correlation New DESTMOL has been developed (Equation 1) to extend TBP curve through molecular
distillation process [4].

AET =-1x10-5TMD3 +0.008xTMD2-0.581xTMD+427 (1)

where: AET = Atmospheric Equivalent Temperature,

TMD = Operating Temperature of the Molecular Distillation Equipment.

The DESTMOL correlation, as it was called, allows conversion of the operating temperature of
molecular distillation in equivalent atmospheric temperatures that are used in the conventional TBP
curves. The extension of TBP curve from DESTMOL correlation reached values next to 973 K, with
continuity and substantial coincidence with the curve obtained from ASTM points.
728 M. S. Lopes et al. / Procedia Engineering 42 (2012) 726 – 732

The molecular distillation process is an efficient method for separation, purification and concentration
of natural products, usually composed of complex and thermally sensitive molecules [4].
Furthermore, this process has advantages over other techniques that use solvents as the separating
agent, avoiding problems with toxicity. Molecular distillation has also been used for heavy petroleum
characterization, demonstrating the potential of this separation process in other applications [5]. It is
characterized by a short exposure of the distilled liquid to elevated temperatures, high vacuum in the
distillation space and a small distance between the evaporator and the condenser [6].
The molecular distillation process must be conducted according to operating conditions and the design
of the equipment is crucial for efficient operation with petroleum residues. Therefore, it was designed and
built up by the petroleum research group of the Separation Process Development Laboratory (LDPS) and
of the Laboratory of Optimization, Design and Advanced Control (LOPCA) at UNICAMP/Brazil, in
partnership with the Laboratory of Valuation of CENPES / PETROBRAS, a falling film molecular
distillation pilot plant suitable to work with heavy petroleum fractions. Operational facilities were
introduced, such as: heating of several pipes to prevent solidification of the product; evaporator with tree
points of heating to establish better control of distillation; automated control system to ensure easiness,
speed and stability in operation. Within this context, the objective of this work is to extend the TBP curve
of three petroleum residues.

Nomenclature
AET tmospheric Equivalent Temperature
TBP True boiling point

2. Experimental

The experiments were performed with three petroleum residues from Brazilian Petroleum Company
(PETROBRAS). These samples came from the bottom of atmospheric tower (atmospheric residue) and
their assumed fantasy names such as Eta Teta and Gama.
The apparatus used was Brazilian laboratory-scale molecular distillation equipment designed by the
research group mentioned in the previous item. The system is a falling film evaporator, shown in Figure 1,
capable of varying flow rates from 0.3 to 5 Kg/h. It is equipped with a short path evaporator, a wiper
basket assembly, a cold trap, a feed vessel, a discharge system and a vacuum pump set. The short path
evaporator is heated in tree separated points with an electric system. It is also attached to an internal
condenser cooled with water. The evaporation and condensation surface areas are 0.11 and 0.10 m2,
respectively. The feed vessel is heated with electrical system. The discharge systems consist of two
separated pipes, one for the distillate, the other one for the residue. The vacuum pumps set consist of a
dual rotary vane pump and an air cooled oil diffusion pump.
The molecular distillation process occurs in steady-state, thus the continuously fed and two product
flows are continuously generated: distillate cuts and residue of molecular distillation. As soon as all
temperatures (feed temperature, evaporator temperature, condenser temperature and product temperatures)
and the vacuum pressure are reached, the wiper system is started. Then, the rotating gear pump feeds the
sample from a heat feed container. Centrifugal gravity forces distribute the material into the inner surface
of the evaporator in the form of a very thin film, with a thickness which will depend on the mixture
viscosity and feeding flow rate. Volatile components vaporize from the film and condense on the cooler
inner condenser. Distillate cuts and residues from molecular distillation are collected separately in
 M. S. Lopes et al. / Procedia Engineering 42 (2012) 726 – 732 729

reservoir cylinders assembled in two carousels. The vacuum pressure (0.1 Pa) in the distiller is set by a
rotary vane pump and a diffusion pump. The residence time depends on the molecular distillation
conditions, especially on the evaporator temperature. It ranges between 5 and 8 min. In this work, a
collecting time of 15 min was used.
A constantly rotating gear pump feeds the sample on a rotating distribution plate from a feed vessel.
The centrifugal force distributes the material on the inner surface of the evaporator, and the gravity makes
it to flow downward; the wiper basket system constantly redistributes it as a very thin film on the
evaporator internal surface. The volatile components of the feed material vaporize from this thin film and
condense on the cooled inner condenser. Distillate and residue streams are each one collected in separated
recipients [7].
The evaporator temperature is the significant variable in the process and it is used in DESTMOL
correlation. Therefore, the experiments were performed in the molecular distillation prototype changing
this temperature. For the Eta, the evaporator temperature was ranged from 413 to 593 K, for the Teta, the
range was from 403 to 593 K, and, for the Gama, the range was from 423 to 608 K.
All these variables were carefully monitored by the controllers present in the falling film molecular
prototype. Each run produced one distilled and one residue cut and they were weighted. The evaporator
temperatures were converted in atmospheric equivalent temperature through Equation 1.
In order to extend TBP curve, these converted data and the distillate weight percentage of each
experimental run were plotted above the TBP curve obtained by standard methods.

Fig. 1. Configuration of falling film molecular distillatory 1 and 2, engine and agitation blades; 3, feeding; 4, condenser; 5, falling
film; 6, evaporator; 7, residue output; 8, distillate output; 9, vacuum system; 10 and 11, cooling fluid; 12 and 13, thermal fluid [8].

3. Results

In Figures 2, 3 and 4 are shown the extended TBP curves of petroleum Eta, Teta and Gama. Data for
extension were determined from the evaporator temperature (converted in AET by the DESTMOL
730 M. S. Lopes et al. / Procedia Engineering 42 (2012) 726 – 732

correlation) and from the distillate weight percentage obtained in each experimental run of molecular
distillation process. These data were associated with standards data to construct the extended TBP curves
of these petroleums. Information about conventional methods, ASTM D2892 and ASTM D 5236, were
provided by CENPES.

Fig. 2. Extended True Boiling Point curve of the petroleum Eta

Fig. 3. Extended True Boiling Point curve of the petroleum Teta.

 M. S. Lopes et al. / Procedia Engineering 42 (2012) 726 – 732 731

Fig. 4. Extended True Boiling Point curve of the petroleum Gama

Using the molecular distillation prototype, it was possible to extend the TBP curve reaching
approximately temperatures of 973 K for each petroleum studied. Furthermore, it can be seen in Figures 2
3 and 4 that the extended data presents continuity and good agreement with the ASTM curves. There was
an increase in the distillate weight percentage for petroleum Eta, Teta and Gama of 11%, 14 % and 10%,
respectively, using the molecular distiller equipment. This is a gain in distillate since the maximum values
achieved by standard methods were lower.

4. Conclusions

The falling film molecular distillation prototype was suitable to work with heavy petroleum residues
without thermal degradation of the materials, i.e., with the physical properties of the compounds
preserved.
The DESTMOL correlation was appropriated to covert the molecular distillation evaporator
temperatures to atmospheric equivalent temperatures, so, extending TBP curves of three petroleum. It
was possible to extend the TBP curves up to temperatures close to 973 K with continuity and good
agreement with the ASTM at lower temperatures curves for these three petroleums.
Regarding to the results obtained, it is possible to obtain Boiling Point at very low pressure using
Molecular Distillation. These data are necessary for obtaining extended TBP curve through Molecular
Distillation, and, so bring important information on petroleum and its characteristics, with very good
precision using the DESTMOL correlation. This is useful to define better strategies and operating
conditions for the petroleum processing, valuing economically heavy petroleum, as for example, in lighter
components and asphalt. The developments achieved in this work are very important since no standard
methodology is available for calculating the TBP extended curve, considering the large amount of
availability of heavy petroleum today encountered.
732 M. S. Lopes et al. / Procedia Engineering 42 (2012) 726 – 732

Acknowledgements

The authors would like to acknowledge FAPESP, CNPq, FINEP and PETROBRAS for the financial
support of this project.

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